Solder ball excellent in micro-adhesion preventing properties and wetting properties and method for preventing the micro-adhesion of solder balls

ABSTRACT

The present invention provides a solder ball that has solved the problem of micro-adhesion and, moreover, has solved both of the problems of micro-adhesion and wetting properties, and a method for preventing the micro-adhesion of solder balls. That is, the present invention provides a solder ball obtained by solidification and spheroidization in a gas phase and having metal soap molecules, preferably a metal soap molecules film of 3 nm or less in thickness, adsorbed on its surface. As the metal soap, there can be used, for example, calcium stearate, magnesium stearate or barium stearate. The present invention is preferably applied to solder balls with a diameter of 400 μm or less. The present invention also provides a method for preventing the micro-adhesion of solder balls which comprises immersing solder balls obtained by solidification and spheroidization in a gas phase, in a solution containing a metal soap dispersed therein, preferably, a solution containing a metal soap dispersed therein to a concentration of less than 5 ppm; taking out the solder balls from the solution; vaporizing the solvent on the surfaces of the solder balls; and then drying the surfaces. The drying is preferably conducted in an atmosphere having a relative humidity RH≦40%.

BACKGROUND OF THE INVENTION

The present invention relates to a solder ball that is excellent inmicro-adhesion preventing properties and wetting properties and is usedfor, for example, the connection of electronic parts; and a method forpreventing the micro-adhesion of solder balls.

At present, electronic parts obtained by mounting a semiconductor or thelike on a substrate are produced by the use of a package having a formcalled BGA (ball grid array) or CSP (chip size package). In theseelectronic parts, solder balls are used for bonding of terminals. Ingeneral, the bonding of the terminals by the use of solder balls isoften conducted in the case of bonding at intervals of hundreds micronsand hence is required to have a high dimensional accuracy. In addition,if unsatisfactory soldering occurs in such bonding of the terminals, thepackage, which is very expensive as compared with the soldering cost,becomes defective. Therefore, the bonding is required to have a highreliability.

For attaining high dimensional accuracy and reliability in the bondingof the terminals, it is important to control the composition of solderballs, soldering conditions and the surface profile of the solder balls.As to the surface profile of the solder balls among them, the degree ofoxidation of the surface has to be low. In producing the package by theuse of solder balls, the solder balls are mounted at predeterminedterminal positions on a BGA substrate and then melted with a heater toform bumps. In this case, if the surfaces of the solder balls are in anoxidized state, the wetting properties of the solder balls at the timeof melting are deteriorated, so that the solder does not completelyadhere to the terminals on the substrate, resulting in an insufficientbond strength. If a film of dirt, an organic substance or the like isformed on the surface of each :solder ball, the wetting properties ofthe solder balls are deteriorated as in the case of an oxide film. Theinsufficient bond strength of the solder results in unsatisfactorysoldering and hence a defective package.

The oxidation of the surfaces of the solder balls is called blackeningbecause the oxidized surfaces of the solder balls look black. As to theproblem of the decrease in bond strength of the solder caused byblackening, there are investigated various methods for suppressing theoxidation of the surfaces of the solder balls by coating the surfaceswith a material different from a material for the solder balls. Theemployment of the following materials as the material for coating thesolder balls is investigated: lubricants such as aliphatic hydrocarbonlubricants, higher aliphatic alcohol higher fatty acid lubricants, fattyamide lubricants, metal soap lubricants, fatty ester lubricants, and thelike (for example, JP-A-2000-288771 (patent document 1)); and rustpreventives such as metals (e.g. Au and Sn) (for example, JP-A-08-164496(patent document 2)).

The coating with any of the above-exemplified lubricants or Ausuppresses the oxidation of the surfaces of the solder balls. Itsconcrete action is as follows. The lubricants have an effect ofinhibiting the surfaces of the solder balls from becoming chemicallyactive owing to wearing-away of the surfaces by their friction with theoutside. In the case of the coating with Au, the oxidation of thesurfaces of the solder balls is suppressed by coating the soldersurfaces with Au that is not easily oxidizable.

On the other hand, in the case of the coating with Sn, the wettingproperties of the solder balls at the time of melting are improved bycoating the solder balls with the metal having high wetting propertiesat the time of melting for a material for the terminals, instead ofsuppressing the oxidation.

In recent years, as a cause for unsatisfactory bonding in the package,the problem of micro-adhesion of solder balls has been pointed out inaddition to blackening. The micro-adhesion of solder balls is aphenomenon remarkably observed in the case of fine solder balls with adiameter of particularly 400 μm or less, more particularly 300 μm orless, and is a state in which originally separated solder balls areadhered to one another by a weak adhesive force. As described above,solder balls have to be mounted on a substrate so that each of them maybe mounted at a predetermined terminal position. The mounting of thesolder balls is conducted with an automated apparatus. in this case, ifthere are solder balls which have undergone micro-adhesion, they are notmounted at terminal positions at which they have to be mounted, or twoor more of them are mounted at any of the terminal positions. As aresult, unsatisfactory bonding is caused in the package.

The coating with any of the materials disclosed in the patent documents1 and 2 reduces the deterioration of the wetting properties at the timeof melting caused by blackening and improves unsatisfactory bonding inthe package caused by this deterioration. These materials are excellentin this regard. However, as a result of investigation by the presentinventors, it was found that the coating with any of the lubricants andthe like cannot solve the problem of the micro-adhesion of solder ballsand, moreover, increases the frequency of the micro-adhesion in somecases.

The present inventors closely investigated the problem of themicro-adhesion of solder balls obtained by solidification andspheroidization in a gas phase, and consequently found that theabove-mentioned micro-adhesion is markedly affected by, in particular, ahumidity to which the solder balls are exposed, and is not easily causedin a dry atmosphere having a low humidity. The present inventorsconfirmed that the various conventional coatings described above reducefriction but accelerate adhesion in some cases. In addition, it wasfound that the wetting properties are deteriorated with an increase ofthe thickness of a coating film formed by any of these coatings.

An object of the present invention is to solve the problem of themicro-adhesion of solder balls and provide a solder ball capable ofbeing given good wetting properties and a method for preventing themicro-adhesion of solder balls.

SUMMARY OF THE INVENTION

The present inventors investigated a method for solving the problem ofthe micro-adhesion by the surface treatment of solder balls, andconsequently found that the adsorption of metal soap molecules on thesurfaces of the solder balls can reduce the occurrence of themicro-adhesion markedly. The present inventors also found that inaddition to this reduction, more satisfactory wetting properties canalso be attained by properly controlling the thickness of a film of themetal soap molecules adsorbed, whereby the present invention has beenaccomplished.

That is, the present invention provides a solder ball obtained bysolidification and spheroidization in a gas phase and having metal soapmolecules adsorbed on its surface, which is excellent in micro-adhesionpreventing properties and wetting properties. The solder ball isprovided as a solder ball possessing further improved wetting propertiesby forming the adsorbed metal soap molecules into a metal soap moleculesfilm of 3 nm or less in thickness. As the metal soap, there can be used,for example, any of calcium stearate, magnesium stearate and bariumstearate. The present invention is preferably applied to solder ballswith a diameter of 400 μm or less.

In the method for preventing the micro-adhesion of solder balls of thepresent invention, solder balls obtained by solidification andspheroidization in a gas phase are immersed in a solution containing ametal soap dispersed therein, and then taken out of the solution, afterwhich the solvent on the surfaces of the solder balls is vaporized andthe surfaces are dried. In addition, more excellent wetting propertiescan be attained by adjusting the concentration of the metal soapdispersed in the solution to less than 5 ppm. The method for preventingthe micro-adhesion of solder balls is preferably as follow: after thevaporization of the solvent on the surfaces of the above-mentionedsolder balls, the surfaces are dried in an atmosphere having a relativehumidity RH≦40%.

According to the present invention, the problem of the micro-adhesion ofsolder balls can be solved and, moreover, satisfactory wettingproperties are retained. Therefore, unsatisfactory bonding in theproduction of a package such as BGA or CSP by the use of solder balls isreduced and, moreover, the wetting properties are retained or improved.As a result, the yield of the package can be improved. Thus, the presentinvention provides an industrially useful technique.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a graph showing the relationship between the concentration ofa metal soap dispersed in a solution for immersing solder balls and thethickness of a film of metal soap molecules adsorbed on the surface ofeach solder ball dried after the immersion.

FIG. 2 is a schematic view showing a method for measuring the frequencyof occurrence of micro-adhesion, which was adopted in Examples.

DESCRIPTIONS OF REFERENCE NUMERALS 1. solder balls, 2. micro-adheredball (solder ball), 3. single ball (solder ball), 4. block for heightadjustment, 5. vat, 6. stand. DETAILED DESCRIPTION OF THE INVENTION

As described above, the solder ball of the present invention ischaracterized by having metal soap molecules adsorbed on its surface,preferably a film with a predetermined thickness of metal soap moleculesadsorbed on the surface. Though the special effect of the metal soap hasnot yet been sufficiently elucidated, it is conjectured as follows.

At first, the problem of the micro-adhesion of solder balls to oneanother is remarkably caused in the case of solder balls obtained bysolidification and spheroidization in a gas phase, but it does noteasily caused in the case of conventional commercial solder ballsproduced by a water-in-oil cooling process comprising solidificationinto balls in-an oil, because of sufficient degreasing. Therefore, it isconjectured that this difference is due to a surface profile differencemade by circumstances of the formation of the balls.

In practice, a solder ball obtained by solidification in a gas phaseforms an oxide layer but this oxide layer has a depth of only about 2.5nm in terms of sputtering rate of SiO₂. Therefore, it can be speculatedthat the surface is active and is very liable to adsorb water in theambient air. When this speculation is combined with the fact that themicro-adhesion is accelerated by the increase of humidity of the ambientair, it is seriously conjectured that the adsorbed water accelerates themicro-adhesion of the solder balls to one another.

On the other hand, in coating the surface, the viscosity and adhesiveproperties of a coating material itself are problem. As a result ofinvestigation by the present inventors, it has been confirmed that nosatisfactory result can be obtained even when a fluororesin having ahigh water repellency is used. Therefore, the present inventorsinvestigated the following: in order not to accelerate the adsorption ofwater, adhesion points are reduced by adsorbing molecules having nopolar group, and as the molecules to be adsorbed, there are usedmolecules having such a structure that they are not easily entwined withone another, whereby the occurrence of adhesion caused by the adsorbedmolecules is prevented. As a result, the present inventors chose a metalsoap.

The metal soap is obtained as follows: a portion of the polar group ofso-called soap, such as Na is replaced by Ba, Mg or the like, so thatthe portion of the polar group is lost, resulting in loss of the surfaceactive properties. On the surface of a solder ball having as an adsorbedportion the metal atom portion of the metal soap having a stronginteratomic force, the nonpolar organic acid portion of the metal soapis present. Therefore, the metal soap is effective in not only reducingadsorption points but also repelling water having a high polarity.Particularly when the organic acid portion of the metal soap is a simplestraight-chain carboxylic acid such as stearic acid, the adhesion,reaction or entwinement of metal soap molecules with one another is noteasily caused. Therefore, such a metal soap is the most suitable.

The frequency of occurrence of the micro-adhesion of solder ballsincreases with a decrease of the diameter of the solder balls. Thereason is conjectured as follows. In the case of solder balls with alarge diameter, even when they undergo micro-adhesion, they are easilyre-separated because the load applied to the adhered portion isincreased by the weight of the solder balls themselves. On the otherhand, in the case of solder balls with a small diameter, when theyundergo micro-adhesion, they are not easily re-separated because theload applied to the adhered portion is light. In addition, it can bespeculated that solder balls with a smaller diameter are more liable toundergo micro-adhesion because their curvature is larger, so that thesurface energy is increased, resulting in an enhanced affinity for watervapor in air. Particularly in the case of solder balls with a diameterof 400 μm or less, more particularly 300 μm or less, the occurrence oftheir micro-adhesion increases but it can be greatly reduced by coatingthe surfaces of the solder balls with a metal soap and drying thesurfaces.

In recent small package .forms such as CSP, further reduction of thepitch of terminals is in progress. The wetting properties of solderballs are important, for example, in the formation of bumps as describedabove. With the above-mentioned reduction of the pitch, good wettingproperties at a smaller amount of a flux used are required in mountingof solder balls on a substrate. At such a slight amount of a flux used,the solder balls come off remarkably when the wetting properties of thesolder balls are not good. Therefore, the solder balls are desired tohave so excellent wetting properties that they can be used even when theamount of a flux used is very small.

Accordingly, the present inventors evaluated wetting properties that arerequired of solder balls. As described above, the solder balls of thepresent invention solve the problem of their mutual micro-adhesion byhaving a film of metal soap molecules adsorbed on the surface of eachsolder ball. On the other hand, it was found that when the film of metalsoap molecules is too thick, the wetting properties of the solder ballsare deteriorated. It was also found that as the thickness of the film ofmetal soap molecules, there is a coating thickness that makes itpossible to solve the problem of the micro-adhesion satisfactorily andis most suitable for the retention and improvement of good wettingproperties. That is, the solder ball of the present invention preferablyhas a film of 3 nm or less in thickness of metal soap molecules adsorbedon its surface.

Here, the above-mentioned coating thickness of the metal soap is definedas follows. The film of metal soap molecules according to the presentinvention as a coating film on the surface of the solder ball exhibitsthe above-mentioned additional effect when its thickness is maintainedat the predetermined thickness. It is not easy to measure the coatingthickness of the metal soap molecules film itself at which theadditional effect is exhibited. Therefore, in the present invention, amethod for accurate specification and description was investigated inorder to reproduce the thickness of the metal soap molecules film atwhich the additional effect is exhibited. As a result, there was adopteda method in which by analyzing the C (carbon) content of the surface ofa solder ball in the direction of surface depth by a combination ofAuger electron spectroscopy (AES) and surface sputtering, the C contentis correlated with the coating thickness of the metal soap moleculesfilm and can be converted to the coating thickness.

The coating thickness of the metal soap molecules film according to thepresent invention has a substantially linear correlation with the amountof C detected which represents the metal soap concentration of asolution for coating treatment described hereinafter. On the other hand,the rate of perforation by sputtering on the surface of a solder ballcan be estimated in terms of SiO₂. For attaining a higher accuracy, theactual depth of perforation has to be estimated in terms of the rate ofperforation of, for example, Sn which constitutes the substance of thesolder ball. However, in the present invention, since there is nostandard capable of permitting calibration (since the preparation of astandard sample is difficult), SiO₂ is employed as a standard sample andthe film thickness of the metal soap is defined as a depth convertedfrom the rate of perforation of SiO₂. When such a method for describingthe coating thickness of the metal soap is adopted, the upper limit of acoating thickness capable of imparting both micro-adhesion preventingproperties and more satisfactory wetting properties according to thepresent invention is 3 nm. The coating thickness is preferably 0.1 to1.5 nm, more preferably 0.1 to 0.8 nm.

The solder ball of the present invention can be obtained, for example,by immersing a solder ball formed by solidification and spheroidizationin a gas phase, in a solution containing a metal soap dispersed therein,taking out the solder ball from the solution, vaporizing a solvent onthe surface of the solder ball, and then drying the surface. For furtherimproving the wetting properties, the thickness of metal soap moleculescovering the solder ball surface after the immersion and drying ispreferably small (the amount of metal soap molecules adsorbed ispreferably small). That is, the upper limit of the concentration of themetal soap in the solution is controlled so as to be preferably 25 ppmor less, more preferably less than 10 ppm. For adjusting the coatingthickness of metal soap molecules to 3 nm (the aforesaid upper limit) orless, the concentration of the metal soap dispersed in the solution ispreferably adjusted to less than 5 ppm.

The concentration of the metal soap dispersed in the above-mentionedsolution is preferably 0.5 ppm or more, more preferably 1 ppm or more,from the viewpoint of the preventive effect of the immersion on themicro-adhesion. However, when the concentration is as too high as about1,000 ppm, the micro-adhesion is accelerated. On the other hand, whenimportance is attached to more excellent wetting properties, theconcentration is preferably 3 ppm or less. As the solvent used fordispersing the metal soap, there can be used, for example, alcoholsolvents, HFE (hydrofluoro ether) solvents such as Novek series solventsmanufactured by SUMITOMO 3M LTD., and solvents comprising a fluoridesuch as C_(n)F_(2(n+1)).

After the vaporization of the solvent, the surface of the solder ball ispreferably further dried in an atmosphere having a relative humidityRH≦40%. This drying is conducted for removing, as much as possible,water molecules adsorbed owing to the solvent or the ambient air duringhandling, by employing the atmosphere having a low relative humidity.The drying is preferably conducted in an atmosphere having a relativehumidity RH≦20%. The drying is preferably conducted for 1 hour or more.

EXAMPLE 1

Under the conditions described below, metal soap molecules were adsorbedon the surfaces of solder balls of Φ3.50 μm and solder balls of Φ300 μmcomposed of 3 mass % of Ag, 0.5 mass % of Cu and the balance of Sn andobtained by solidification in a gas phase, and the surfaces were dried,after which the frequency of occurrence of micro-adhesion was estimated.

Treating Agents:

-   -   barium stearate (present invention example 1),    -   magnesium stearate (present invention example 2),    -   calcium stearate (present invention example 3)

-   Solvent: C₅F₁₂ fluoride type solvent

-   Concentration: 500 ppm    Method: immersion for 300 seconds, followed by vaporization of the    solvent at 40° C. for 600 seconds (thermostatic chamber)    Drying Conditions:    -   atmosphere: relative humidity RH=10%, room temperature RT=24° C.    -   drying (standing) time: 10 hours.

The frequency of occurrence of micro-adhesion was estimated by a methodin which as schematically shown in FIG. 2, a vat 5 was tilted at anangle of 0.2° to the horizontal plane with a block for height adjustment4 and a stand 6 was vibrated to roll solder balls 1 on the plane of thevat 5. As shown in FIG. 2, when the solder balls 1 were rolled on thevat 5, a solder ball that had not undergone micro-adhesion (the singleball 3 in FIG. 2) went straight downward, while most of solder ballsthat had undergone micro-adhesion (the micro-adhered balls 2 in FIG. 2)did not go straight, The number (the number of groups) of micro-adheredballs among about 1,900 solder balls was counted by a method comprisingvisually confirming the micro-adhered balls 2 that did not go straightdownward.

For comparison, the same estimation as above was carried out also forsolder balls not treated at all (comparative example 1) and solder ballscoated with sodium stearate (comparative example 2). The coating withsodium stearate was conducted under the following conditions:

Coating Conditions for (Comparative Example 2)

-   -   Treating agent: sodium stearate    -   Solvent: isopropyl alcohol    -   Concentration: 500 ppm    -   Method: immersion for 600 seconds, followed by vaporization of        the solvent at 50° C. for 600 seconds (thermostatic chamber)

Drying conditions: the same as for the present invention examples 1 to3. TABLE 1 Present Present Present invention invention invention example1 example 2 example 3 φ350 φ300 φ350 φ300 φ350 φ300 Treating agent Bastearate Mg stearate Ca stearate Number of groups 0 6 0 0 0 2 ofmicro-adsorbed solder balls (groups) Frequency of 0.00 0.32 0.00 0.000.00 0.01 occurrence (%)

TABLE 2 Comparative Comparative example 1 example 2 φ350 φ300 φ350 φ300Treating agent None Na stearate (no treatment) Number of groups 41 52 1827 of micro-adsorbed solder balls (groups) Frequency of 2.15 2.73 0.951.42 occurrence (%)

As can be seen from the results shown in Table 1 and Table 2, theoccurrence of micro-adhesion is greatly reduced in the case of both thesolder balls of Φ350 μm and solder balls of Φ300 μm of the presentinvention examples, which had metal soap molecules adsorbed thereon, ascompared with the untreated solder balls of comparative example 1. Onthe other hand, the frequency of occurrence of micro-adhesion is reducedin the case of the solder balls coated with so-called soap ofcomparative example 2 as compared with the untreated solder balls ofcomparative example 1, but the reduction is not sufficient.

EXAMPLE 2

Metal soap molecules were adsorbed on the surfaces of solder balls ofΦ300 μm composed of 3 mass % of Ag, 0.5 mass % of Cu and the balance ofSn and obtained by solidification in a gas phase, by immersing thesolder balls in each of solutions containing various concentrations ofthe metal soap, and the surfaces were dried. Magnesium stearate was usedas the metal soap and the treating and drying conditions other than theconcentrations of the metal soap in the solutions were the same as inthe case of the present invention examples 1 to 3. Mounting of the thustreated solder balls on a substrate and their reflow were tested underthe conditions described below, to estimate their wetting properties atthe concentrations of the metal soap in the solutions.

As to the mounting conditions and reflow conditions, a water-solubleflux was applied by pin transfer on a substrate having a plated Ni/Aufilm formed on one side, as a very small amount of a flux for an assumednarrow pitch, and the solder balls were mounted thereon. The reflow wascarried out at 220° C. or higher (the highest: 240° C.) for 60 secondsand the spread-of-wetting ratio [=√ (spread-of-wetting area/ theprojected area of the ball)] in this case was measured. The higher thespread-of-wetting ratio, the higher the wetting properties. TABLE 3 Mgstearate concentration 5 ppm 8 ppm 25 ppm 150 ppm 500 ppm Spread-of- 4.13.9 2.8 2.1 1.8 wetting ratio

It can be seen that the micro-adhesion of the solder balls having metalsoap molecules adsorbed thereon can be markedly suppressed and that asshown in Table 3, these solder balls also have excellent wettingproperties when the metal soap concentration in the immersion for theadsorption is adjusted to the optimum concentration.

EXAMPLE 3

Under the conditions described below, metal soap molecules were adsorbedon the surfaces of solder balls of Φ300 μm composed of 3 mass % of Ag,0.5 mass % of Cu and the balance of Sn and obtained by solidification ina gas phase and the surfaces were dried. Then, the frequency ofoccurrence of micro-adhesion was estimated.

Treating Agents:

-   -   barium stearate (present invention example 4),    -   magnesium stearate (present invention example 5),    -   calcium stearate (present invention example 6)

-   Solvent: C₅F₁₂ fluoride type solvent

-   Concentrations: six concentrations of 0, 1.0, 3.0, 4.5 10 and 50 ppm    Treating conditions: immersion for 180 seconds, followed by drying    by vaporization of the solvent at a relative humidity RH of 10% and    at room temperature RT of 22° C.

At first, there was measured the thickness of a film of metal soapmolecules adsorbed on the surface of each of the solder balls treated ateach of the aforesaid six concentrations, after the aforesaid drying byvaporization. The measurement was carried out by the above-mentionedmethod comprising analysis of the C content in the direction of surfacedepth by a combination of AFS and sputtering. The results obtained areshown in FIG. 1, a log-log graph.

From FIG. 1, it can be seen that in the case of all the metal soaps,there is a linear correlation between the concentration of each metalsoap as solute and the thickness of the adsorption film after theimmersion and drying and that the thickness of the adsorption film canbe controlled by adjusting the concentration of the metal soap in asolution for the immersion.

Then, the frequency of occurrence of micro-adhesion was estimated. Theestimation was carried out in the same manner as that described inExample 1 and shown in FIG. 2, namely, the estimation was carried out bycounting the number (the number of groups) of micro-adhered balls amongabout 100,000 solder balls. The experimental results are shown in Table4. TABLE 4 Number of micro-adsorbed solder balls Solute concentration(ppm) (balls) 0 1.0 3.0 4.5 10 50 Ca stearate 30 [—] 9 [0.27] 7 [0.5] 7[0.8] 5 [3.2] 4 [16] Mg stearate ↑ [—] 7 [0.15]  4 [0.83] 2 [1.5] 2[2.5]   1 [13.2] Ba stearate ↑ [—] 6 [0.28] 4 [0.7]  3 [1.13] 2 [2.3] 1[10]Each value in [ ] after the number of micro-adhered solder balls is acoating thickness value (nm) measured by employment of AES.

In addition, the wetting properties were evaluated by mounting thesolder balls on pads coated with a very small amount of a flux on a BGAsubstrate, subjecting them to reflow treatment under a nitrogenatmosphere, and observing the degree of wetting by the balls. Theevaluation conditions are as follows:

-   Pad; diameter: 240 μm, ground: an electroless plated Ni film,    surface: a flash-plated Au film, the number of pads: 1:00-   Flux; a water-soluble flux WS-9160-M3 (mfd. by Alpha Metals Co.,    Ltd.), applied in an amount of 0.0004 mm³ with a dispenser-   Reflow conditions; N₂ atmosphere, preheating; 150-170° C./180    seconds+220° C. or higher/60 seconds (peak temperature: 240° C.).

As to the judgment of the wetting properties, the pads after the reflowwere classified into following three groups: pads the whole surface ofwhich was wetted and which showed a satisfactory bump shape; pads partlywetted and showing a distorted bump shape; and pads not wetted at all.Then, the percentage of bumps having a satisfactory shape wascalculated. The experimental results are shown in Table 5. TABLE 5Percentage of satisfactory Solute concentration (ppm) bumps (%) 0 1.03.0 4.5 10 50 Ca stearate 100 [—] 100 [0.27] 100 [0.5] 95 [0.8] 90 [3.2]70 [16] Mg stearate ↑ [—] 100 [0.15]  100 [0.83] 100 [1.5]  91 [2.5]  75 [13.2] Ba stearate ↑ [—] 100 [0.28] 100 [0.7] 100 [1.13] 93 [2.3]80 [10]Each value in [ ] after the percentage of satisfactory bumps is acoating thickness value (nm) measured by employment of AES.

From Table 4, it can be seen that in spite of the kind of the metal soapused, the occurrence of micro-adhesion can be greatly reduced in thecase of solder balls of Φ300 μm having a large coating thickness ortreated by the immersion at a high solute concentration, as comparedwith solder balls of Φ300 μm subjected to no coating treatment, namely,those corresponding to a solute concentration of 0 ppm. For reducing thenumber of micro-adhered solder balls, the solute concentration ispreferably as high as possible, though the effect of the increase of thesolute concentration substantially reaches a point of saturation at 10ppm.

On the other hand, it can be seen from FIG. 5 that with a decrease ofthe coating thickness or a decrease of the solute concentration employedin the immersion, the wetting properties and the bump shape areimproved. When the solute concentration is 3 ppm or less, good wettingproperties can be attained which are equal to wetting propertiesattained without the coating treatment. The suitable upper limit of thesolute concentration is 3 ppm. The coating thickness is suitably 0.8 nmor less.

It can be seen that solder balls satisfying the desirable requirementsof the present invention with respect to the coating thickness of metalsoap molecules or the solute concentration employed in the immersionhave both good micro-adhesion preventing properties and good wettingproperties. For attaining both of them, the suitable range of the soluteconcentration is 0.5 to 3 ppm and that of the coating thickness is 0.1to 0.8 nm.

1-4. (canceled)
 5. A method for preventing the micro-adhesion of solderballs which comprises immersing solder balls obtained by solidificationand spheroidization in a gas phase, in a solution containing a metalsoap dispersed therein, taking out the solder balls from the solution,vaporizing the solvent on the surfaces of the solder balls, and thendrying the surfaces.
 6. A method for preventing the micro-adhesion ofsolder balls according to claim 5, wherein the solder balls obtained bysolidification and spheroidization in a gas phase are immersed in asolution containing a metal soap dispersed therein to a concentration ofless than 5 ppm.
 7. A method for preventing the micro-adhesion of solderballs according to claim 5, wherein the solvent on the surfaces of thesolder balls is vaporized and then the surfaces are dried in anatmosphere having a relative humidity RH≦40%.
 8. A method for preventingthe micro-adhesion of solder balls according to claim 6, wherein thesolvent on the surfaces of the solder balls is vaporized and then thesurfaces are dried in an atmosphere having a relative humidity RH≦40%.